Silver halide photographic elements containing phenol or naphthol carboxylic acid amide couplers

ABSTRACT

IMPROVED CYAN IMAGES ARE PRODUCED BY PHOTOGRAPHIC COLOR DEVELOPMENT WHEN THE CYAN COUPLER IS A SUBSTITUTED 1-PHENOL-2-CARBOXYLIC ACID AMIDE OF THE FOLLOWING FORMULA   2-(R-NH-CO-N(-R)-(CH2)N-NH-CO-)PHENOL   WHEREIN N=1-6 AND R IS ALKYL OR ARYL.

United States Patent Olhce Claims priority, applicatitsmzGermany, Dec.2, 1966,

4 47 Int. Cl. cine 7/00 US. CI. 96-55 5 Claims ABSTRACT OF THE DISCLOUREImproved cyan images are produced by photographic color development whenthe cyan coupler is a substituted 1-phenol-2 carboxylic acid amide ofthe following formula wherein n: l6 and R is alkyl or aryl.

This is a continuation of my copending application Ser. No. 686,723,filed Nov. 29, 1967, for Improved Colour- Photographic Images, nowabandoned.

This invention relates to a process for producing photographic colorimages by colorforming development, and to a photographic material forcarrying out this process.

It is common practice to produce the cyan partial image by means ofphotographic materials containing color couplers of the phenol ornaphthol series. Although many cyan couplers are known, none of themsatisfies all the various requirements for such couplers. On thecontrary, most color couplers sufier certain serious disadvantages. Lackof stability of the residual coupler which was not coupled with thecolor developer in producing the dye image, often leads to discolorationin the white areas of the image. Moreover, the dyes produced uponcolorforming development usually show undesirably high side absorptions.Many couplers yield dyes in the form of relatively coarse dye grains,whilst, with others, the coupling reaction is too slow. Generallyspeaking, the cyan dyes obtained by oolorforming development showinadequate fastness to light, and unsatisfactory resistance tohydrolysis and undesired sensitivity to reducing agents.

It is among the objects of the present invention to provide cyancouplers which form upon colorforming development dyes with improvedabsorption properties and increased resistance to chemicals.

I now have found that compounds corresponding to the following formula3,585,035 Patented June 15, 1971 for example by hydroxyl, phenyl,halogen such as chlorine or carboxyl, and the like; (II) aryl inparticular a radical of the phenyl series, which phenyl group may besubstituted for example by halogen such as fluorine, chlorine orbromine, alkyl in particular short-chain alkyl with up to 3 carbonatoms, such as methyl or ethyl, substituted alkyl, for examplehalogen-substituted alkyl, such as trifluoromethyl, carboxyl, esterifiedcarboxyl, alkoxy with preferably up to 5 carbon atoms or aroxy such asphenoxy, sulto;

R may represent for example 4 chlorophenyl, 4 ethoxyphenyl, 4methylphenyl, 2 methylphenyl, 2.4 dimethylphenyl, 3.5 dimethylphenyl,3.5 dicarboxyphenyl, 4 carboxyphenyl, 2 ethoxyphenyl or 3,5bistrifluoromethylphenyl radicals:

R represents (1) alkyl with up to 18 carbon atoms such as methyl, ethylor stearyl, which alkyl radicals may be substituted for example by ahydroxyl group, a halogen atom such as fluorine, chlorine or bromine, ora sulfo group; (II) an alkenyl radical with up to 17 carbon atoms; (III)an aryl radical preferably a radical of the phenyl series, which arylgroup may be substituted, for example by alkyl with up to 18 carbonatoms such as methyl or dodecyl, (IV) an amino group and in partic ularan alkylor aryl-substituted amino group such as stearylamino,dodecylphenylamino or myristylamino, (V) an alkoxy radical or (VI) anaroxy radical preferably phenoxy in which case the phenyl group may besubstituted for example with alkyl with up to 18 carbon atoms, halogensuch as fluorine, chlorine or bromine, alkoxy, carboxy, esterifiedcarboxyl or sulfo;

12 represents hydrogen or the ring members, necessary for completing afused aryl ring preferably a phenyl ring or a fusedtetrahydrocarbocyclic ring preferably a tetrahydrobenzene ring;

n=l to 6 and preferably 3.

Particular utility is exhibited for example by the following colorcouplers:

The color couplers according to the invention are pre pared in a mannerknown per se. A process for their preparation is described in detail inthe following:

Coupler II 372 g.(4 mols) of aniline and 26 ml. of glacial acetic acidare heated to 125 C. in a three-necked flask provided with a refluxcondenser. 276 g.(5 .2 mols) of acrylonitrile are then added dropwisewith stirring over a period of 5 hours at a bath temperature of around130 C., causing the internal temperature to drop to 100 C. Stirring iscontinued while the bath temperature gradually rises until the internaltemperature is 132l34 C. The reaction mixture is then distilled invacuo. After the first runnings of unreacted material, 411 g. of crudeproduct of B.P. =185190 C. are collected. The crude product is purifiedby stirring it with a mixture of 400 ml. of water and 400 ml. ofhydrochloric acid, filtering off the undissolved component in thepresence of active carbon and adding at 10-15 C. a solution of 200 g. ofcaustic soda in 1200 ml. of water. The product is filtered under suctionand washed with water, dried in vacuo and then distilled under a highvacuum. 340 g. of pure ,B-anilinopropionitrile of B.P. =ll2-1 14 C. M.P.54 C. are obtained.

43.8 g. (0.3 mol) of fl-anilinopropionitrile are stirred with 79.2 g.(0.3 mol) of naphthsalol (phenyl l-hydroxy- 2-naphthoate) in athree-necked fllask and fused at 120 C., the product being stirred foranother 5 hours at 160 C. It is then cooled to 80 C. and stirred intowater. The precipitate which forms is recrystallised from methanol inthe presence of active carbon and then from benzene/ petroleum ether. 69g. of 1-hydroxy-N-phenyl-N-betacyanoethyl-2-naphthoylamide melting at128 l30 C. are obtained.

56 g. of ammonia gas are dissolved in a solution of 156 g. of 1 hydroxyN phenyl-N-betacyanoethyl-Z- naphthoylamide in 1560 ml. of methanol and440 ml. of ethanol. The resulting solution is hydrogenated at 80 C./50atms. in the presence of 78 g. of Raney nickel. On completion ofhydrogenation, the product is separated from the catalyst by filtration.The filtrate which is still warm is then adjusted with concentratedhydrochloric acid to pH 4 and precipitated ammonium chloride isfiiltered off. Upon evaporation of the resulting solution to a smallvolume and cooling, a deposit is formed, which is filtered off undersuction and stirred twice with soda solution. The free base thusprecipitated in suction-filtered, dried and recrystallized frommethanol. 120 g. of l-hydroxy-N- omegaphenylarninopropyl 2naphthoylamide melting at 130-131 C. are obtained.

24 g. of 1 hydroxy N omegaphenylaminopropyl-Z- naphthoylamide (0.075mol) are dissolved in ml. of dried tetrahydrofuran in a three-neckedflask equipped with condenser and stirrer and 21.2 g. of stearylisocyanate are added dropwise to the resulting solution. Stirring iscontinued for 5 hours at C., after which most of the solvent isdistilled 01f again. The reaction mixture is crystallized by mixing withcold water. Thereafter, it is suction-filtered, the residue dried andfinally recrystallized from methanol. 38 g. of coupler -II melting at63-64 C., are obtained.

In order to vary R in the general formula the acrylonitrile may bereacted with a variety of amines. A report of such addition reactionscan be found in Houben-Weyl, vol. nitrogen compounds II, page 274.Hitherto, these reactions have only been possible by the addition ofcatalysts such as carbazolpotassium (cf. Houben-Weyl) or choline hydrate(cf. Pietra, Gazzetta Chimica Italiana, volume 86, page 70 [1956] or bythe addition of acids (cf. British patent specification No. 466,316[1936]; Chemisches Zentralblatt 1937, II, 2750).

Coupler XVII N-(Z-hydroxyethyl)-ethylene diamine is fused withnaphthsalol and the product reacted with stearyl isocyanate and couplerXVII is obtained.

Coupler XVIII Bromoethylamine hydrobromide is reacted with 2-methyl-aniline. The N-(Z-methylanilino)-ethylene diamine thus formed ismelted twith naphthsalol, the resulting compound is reacted withdodecylphenylisocyanate and the color component is sulfonated in thefinal stage to form color coupler XVIII.

Coupler XIX The addition product of 4-ethoxyaniline and acrylonitrile ishydrogenated with Raney nickel in a solution of ammonia in methanol togive N-ethoxyphenyl trimethylene diamine which, after purification byvacuum distillation, is reacted with naphthsalol by melting therewith. Along chain fatty group is introduced by reaction with stearylisocyanate.

Coupler XX Bromoethylamine hydrobromide is reacted in pyridine with2,4-dimethyl aniline to form N-2,4-dimethylphenyl ethylene diamine whichis melted with naphthsalol. A long chain fatty group is introduced intothe reaction product by reaction with 3-lauryl0xypropylisocyanate.

Coupler XXI Tetramethylene diamine is reacted with 2-hydroxyethyliodidein pyridine to form N-(Z-hydroxyethyl)-tetramethylene-1,4-diamine.

Coupler XXII Bromoethylamine hydrobromide is reacted in pyridine with3,5-dicarbethoxyaniline to form N-,(3,4-dicarbethoxyphenyl)-ethylenediamine. This reaction product is melted with naphthsalol atapproximately C. After the next reaction with octadecyl isocyanate, thetwo ester groups are carefully hydrolysed.

The color couplers according to the invention may be incorporated in thelight-sensitive silver halide emulsion layers in diffusion-resistantform. This can be performed in known manner by dissolving color couplerssubstituted by long alkyl radicals and water-solubilising groups, in thecasting solution.

According to another known method, solutions of the color couplers whichare hydrophobic, may be emulsified if desired in the presence ofso-called oil formers, in gelatinc, after which the resulting emulsionis dried, and allowed to swell again in water and is then mixed with thesilver halide gelatine emulsion. Other processes are known according towhich the solution of the color coupler in an organic solvent is mixeddirectly with the silver halide emulsion, and the solvent is evaporatedoff. The color couplers according to the invention may be used in any ofthese processes.

The new dye components may be added not only to the light-sensitivesilver halide emulsion layer itself, but also to an adjacentnon-sensitive layer. The concentration of the coupler in thelight-sensitive halide emulsion layer is not critical and depends on theetfect desired, the type of silver halide emulsion etc. An amount of 1g. to 15 g. per liter of emulsion ready for casting has generally provedsufficient.

The coupler may also be developed into the photographic material inconjunction with the color developer.

Light-sensitive layers containing the color couplers according to theinvention will generally be used in multilayer materials although layersof this kind may of course also be used as a single layer on a suitablesupport.

Any color developers containing a primary amino group may be used fordevelopment, although those of the pphenylene diamine series arepreferred. Examples of these are N,N-diethyl-p-phenylene diamine,N-monomethyl-pphenylene diamine, N,N-dimethyl-p-phenylene diamine, 2-amino-S-diethylaminotoluene and N-butyl-N-w-sulfobutyL p-phenylenediamine.

Suitable binding agents for the layers include conventional hydrophilicfilm formers such as proteins, in particular gelatine, polyvinylalcohol, polyvinylpyrrolidone, cellulose derivatives such ascarboxyalkyl cellulose, in particular carboxymethyl cellulose,derivatives of alginic acid and their alkali metal salts or esters.

The cyan couplers according to the invention are preferably added tored-sensitized photographic silver halide emulsions. In addition,emulsions of this kind may contain chemical sensitizers in the usualway. These layers may also be stabilized by use of conventionaladditives and in particular by the azaindene derivatives described byBirr in Z. wiss. Phot. 47 (1952), pages 2 to 28.

EXAMPLE 1 3 g. of color coupler XVII are made into a paste with 4 ml. ofethanol. 4% sodium hydroxide is added to the mixture in such a quantitythat the pH-value rises to 89, after which the product is made up withwater to 150 ml. giving a solution which is stirred into 300 g. of aphotographic silver bromide gelatine emulsion. This emulsion wasprepared by mixing 75 g. of a starting emulsion prepared from 70 g. ofAgNO per kg. and 225 g. of 7.5% gelatine solution. The casting viscositycan be adjusted by adding a little water. This mixture is applied in theusual way onto a transparent cellulose acetate support and dried.

The photographic material thus prepared is imagewise exposed and thendeveloped in a colorforming developing bath of the followingcomposition:

G. N,N-diethyl-p-phenylenediamine hydrochloride 2.75 Anhydrous sodiumsulfite 2 Potassium carbonate 75 Potassium bromide 0.5 Hydroxylaminehydrochloride 1.2 Sodium hexametaphosphate 1.0

Water up to 1000 ml.

The exposed and developed material is bleached, fixed and rinsed withWater in the usual way. A cyan dye image with an absorption maximum at686 m is obtained.

Similar results are obtained with color components XX.

EXAMPLE 2 3 g. of color coupler II are dissolved in 15 ml. of ethylacetate at 5560 C. The resulting solution is added to 50 ml. of 5%gelatine to which 8 g. of lauryl sulfate per kg. have been added asstabilizer, and the resulting mixture is emulsified. 50 g. of thephotographic silver bromide gelatine emulsiondescribed'in Example 1 are6 added to this emulsion while it is still warm. The mixture is dilutedwith 100 ml. of 7.5% gelatine solution and then applied in the usual wayonto a cellulose acetate support and dried.

After exposure and development in the developer solution described inExample 1, bleaching, fixing and rinsing with water in the usual way, acyan dye image is obtained which has an absorption maximum at 673 me.

After exposure, a dye image may also be obtained by use of the followingdeveloper solution:

Benzyl alcohol3.8 ml.

Sodium hexametaphosphate-2 g.

Anhydrous sodium sulfite2 g.

Sodium hydroxide 10% )--5.5 ml.

2-amino-5 [N ethyl N (s methylsulfonamidoethyl)'-amino]-toluene-sesquisulfate monohydrate-S g.

Potassium bromide-l g.

Sodium carbonate monohydrate50 g.

Water up to 1000 ml.

pH-value at 21 C. 10.75

After bleaching, fixing and rinsing with water in the usual way, a cyandye image is obtained which has an absorption maximum at 698 mComparison of this dye with cyan dyes of the kind commonly used in theart for example the dye obtained from l-hydroxy-Z-naphthoylstearylamide, with the abovementioned developer shows that the colorgrain of the dye according to the invention is appreciably finer.

The dye is not affected after standing for 24 hours at 60 C. and 96%relative atmospheric humidity. In contrast, 40% of the comparison dye isdestroyed at a density of 0.5 under such conditions.

If a sample is allowed to stand for 24 hours at 14 mm. pressure and C.,the dye is not affected, whilst 30% of the comparison dye is destroyedat a density of 0.5.

If the dye is exposed to light together with the comparison dye, nochanges are visible in the dye from the color coupler according to theinvention, whereas the comparison dye is partially bleached out.

What is claimed is:

1. In a process of making color photographic images by exposing alight-sensitive photographic material comprising at least onelight-sensitive silver halide emulsion layer, color-forming developmentin the presence of a color coupler, bleaching and fixing, theimprovement consisting of performing the colorforming development in thepresence of a cyan coupler of the formula:

in which R is a hydrogen or halogen atom or a sulfo group which may bepresent in salt form;

R is a hydrogen;

R is an alkyl group or a radical of the phenyl series;

R represents an alkyl substituted amino group or an aryl substitutedamino group;

b represents hydrogen atom or the ring members neces sary for completinga fused phenyl ring which may be tetrahydrogenated; and

rv=1 to 6.

2. A process as claimed in claim 1, wherein n=3.

3. A process as claimed in claim 1, wherein before the exposure thecolor coupler is added to a photographic emulsion layer, which issensitized to red.

8 4. A light-sensitive photographic material comprising necessary forcompleting a fused phenyl ring which at least one silver halide emulsionlayer, which contains may be tetrahydrogenated; and a cyan coupler ofthe following formula: 11:1 to 6.

OH 5. A light-sensitive photographic material as claimed 1] (i 5 inclaim 4, wherein n=3. b- CN CH u N"" R 2) l 4 References Cited b- 2 3UNITED STATES PATENTS 10 3,135,609 6/1964 Klinger 96-1OO R1 3,328,4196/1967 Anderson 96100 1n whlch 3,337,344 8/1967 Kimura et a1. 96100 1 15a hydrogen, halogen or a sulfo group which y 3,418,129 12/1968 Kimura eta1. 96100 be present in salt form; R is hydrogen; J. TRAVIS BROWN,Primary Examiner R is an alkyl group or a radical of the phenyl series;15 R represents an alkyl substituted amino group or an C X- arylsubstituted amino group; 9610() b represents a hydrogen atom or the ringmembers

